Plastic-coated mercaptosilane/wax mixture

ABSTRACT

The invention relates to a plastics-covered mercaptosilane-wax mixture, where the plastic of the plastics covering is selected from the group of polypropylene, polyethylene, ethylene-vinyl acetate copolymer and mixtures of the abovementioned plastics with melting point from 70 to 170° C., and the mercaptosilane-wax mixture comprises at least one mercaptosilane of the general formula I 
                         
and at least one wax with congealing point from 30 to 160° C.
 
     The plastics-covered mercaptosilane-wax mixture can be used in rubber mixtures.

The invention relates to plastics-covered mercaptosilane-wax mixtures,processes for production of these, and also to use of these.

In the tyre industry sulphur silanes are sometimes used in order, incombination with silica, to improve rolling resistance, wet skidperformance and abrasion resistance. The sulphur silanes normally usedare liquid, and introduction of these therefore requires that the liquidsilane be weighed out in advance and sealed within an envelopingmaterial or that liquid is metered directly into the mixer. In order toavoid this type of complicated addition method, it is possible to absorbthe sulphur silanes onto a carrier. The intention is that the carrierdoes not react with the sulphur silane, i.e. is chemically inert, inorder that the entire amount of silane is available within the tyremixture.

EP 1285926, EP 1683801 and EP 1829922 disclose mercaptosilanes orpolysulphidic silanes having polyether groups. The silanes can also havebeen absorbed on an organic carrier.

Furthermore, KR 850000081 discloses silane/filler blends and WO2013149790 discloses mercaptosilane/carbon black blends.

U.S. Pat. No. 7,078,551 moreover discloses blocked mercaptosilanes on acarrier.

DE 102013203651 discloses mercaptosilane-polymer mixtures.

The known mercaptosilane/carrier mixtures have a disadvantageous shelflife.

It is an object of the present invention to provide mercaptosilaneswhich have good shelf life and processability.

The invention provides a plastics-covered mercaptosilane-wax mixturewhich is characterized in that the plastic of the plastics covering isselected from the group of polypropylene, polyethylene, preferably LDPE,ethylene-vinyl acetate copolymer and mixtures of the abovementionedplastics with melting point from 70 to 170° C., preferably from 85 to140° C., particularly preferably from 100 to 120° C., and themercaptosilane-wax mixture comprises at least one mercaptosilane of thegeneral formula I

where R¹ is an alkyl polyether group —O—(R⁵—O)_(m)—R⁶, where R⁵ isidentical or different and is a branched or unbranched, saturated orunsaturated, aliphatic divalent C1-C30 hydrocarbon group, preferablyCH₂—CH₂, CH₂—CH(CH₃), —CH(CH₃)—CH₂— or CH₂—CH₂—CH₂, m is on average from1 to 30, preferably from 2 to 20, particularly preferably from 2 to 15,very particularly preferably from 3 to 10, extremely preferably from 3.5to 7.9, and R⁶ is composed of at least 1, preferably from 11 to 30,particularly preferably from 12 to 20, C atoms and is an unsubstitutedor substituted, branched or unbranched monovalent alkyl, alkenyl, arylor aralkyl group,R² is identical or different and is an R¹, C1-C12-alkyl or R⁷O group,where R⁷ is H, methyl, ethyl, propyl, C9-C30 branched or unbranchedmonovalent alkyl, alkenyl, aryl, or aralkyl group or (R⁸)₃Si group,where R⁸ is C1-C30 branched or unbranched alkyl or alkenyl group,R³ is a branched or unbranched, saturated or unsaturated, aliphatic,aromatic or mixed aliphatic/aromatic divalent C1-C30, preferably C1-C6,particularly preferably C3, hydrocarbon group andR⁴ is H, CN or (C═O)—R⁹, where R⁹ is a branched or unbranched, saturatedor unsaturated, aliphatic, aromatic or mixed aliphatic/aromaticmonovalent C1-C30, preferably C5 to C30, particularly preferably C5 toC20, very particularly preferably C7 to C15, extremely preferably C7 toC11, hydrocarbon group,and at least one wax, preferably paraffinic wax, particularly preferablya mixture of different paraffinic waxes, with particular preference amixture or n- and iso-paraffinic waxes, with congealing point from 30 to160° C., preferably from 40 to 130° C., particularly preferably from 60to 80° C.

The melting point of the plastic is determined in accordance with ISO3146:2000.

The congealing point of the wax is determined in accordance with DIN ISO2207.

The plastics covering can comprise >90% by weight of plastic, preferably≥95% by weight, particularly preferably >97% by weight. The plasticscovering can be composed of polypropylene, polyethylene, preferablyLDPE, ethylene-vinyl acetate copolymer of a mixture of theabovementioned plastics.

The plastics covering can cover the mercaptosilane-wax mixture entirely.

The plastics covering can preferably be a plastics sachet.

The glass transition temperature of the plastic can be from −80 to +10°C. Particularly preferred glass transition temperatures can be:ethylene-vinyl acetate from −30 to −10° C., polyethylene from −100 to−20° C. and polypropylene from −30 to +10° C.

Glass transition temperature can be determined in accordance with DIN ENISO 11357-2.

The average molar mass of the plastic can be from 50 000 to 1 000 000g/mol, preferably from 80 000 to 500 000 g/mol, particularly preferablyfrom 100 000 to 250 000 g/mol. Average molar mass can be determined inaccordance with DIN EN ISO 16014-5.

The melt flow rate (MFR) of the plastic can be from 0.2 to 30 g/10 min(DIN EN ISO 1133: 190° C./2.16 kg). Particularly preferred melt flowrates can be: ethylene-vinyl acetate from 0.4 to 1.0 g/10 min,polyethylene from 1.0 to 5.0 g/10 min and polypropylene from 20 to 30g/10 min.

The ethylene-vinyl acetate copolymer is a copolymer of vinyl acetate andethylene and can comprise from 4 to 30% by weight, preferably from 4.3to 6.7% by weight, of vinyl acetate (DIN EN ISO 4613-2).

The polyethylene plastic can be HDPE or LDPE. The melting point of theLDPE plastic can be from 105° C. to 130° C. The melting point of theHDPE plastic can be from 125° C. to 150° C. The melting point of thepolypropylene plastic (PP) can be from 140 to 170° C., and the meltingpoint of the ethylene-vinyl acetate copolymer can be from 70° C. to 125°C.

The polyethylene plastic can be an LDPE with density from 0.915 to 0.935g/cm³ or an HDPE with density from 0.94 to 0.97 g/cm³. The density ofthe polypropylene can be from 0.895 to 0.92 g/cm³. The density of theethylene-vinyl acetate copolymer can be from 0.92 to 1.0 g/cm³. Thedensity of the plastic can be determined in accordance with DIN EN ISO1183.

The thickness of the plastics covering, preferably the plastics sachet,can be from 10 to 3000 μm, preferably from 40 to 1000 μm, particularlypreferably from 100 to 250 μm.

The water-vapour transmission of the plastics covering, preferablyplastics sachet, can be less than 10 g/(m²d), preferably less than 5g/(m²d), particularly preferably less than 1 g/(m²d), at 85% r.h. and23° C. The oxygen transmission of the plastics covering, preferablyplastics sachet, can be less than 15 000 cm³/(m² d bar), preferably lessthan 10 000 cm³/(m² d bar), particularly preferably less than 3000cm³/(m² d bar), at 85% r.h. and 25° C.

Water-vapour transmission can be determined in accordance with DIN53122-2.

Oxygen transmission can be determined in accordance with DIN 53380-2.

The mercaptosilane-wax mixture can comprise, based on themercaptosilane-wax mixture, at least 10% by weight, preferably at least40% by weight, particularly preferably from 70% to 95% by weight, veryparticularly preferably from 80 to 85% by weight, of mercaptosilane ofthe general formula I.

The ratio by weight of mercaptosilane of the general formula I to waxcan be from 10:90 to 95:5, preferably from 55:45 to 90:10, particularlypreferably from 80:20 to 85:15.

The needle penetration of the wax used can be from 14 to 26 1/10 mm,preferably from 15 to 20 1/10 mm at 25° C.

Needle penetration can be measured in accordance with DIN 51579.

The mixture of n- and iso-paraffinic waxes may have a weight ratio of n-to iso-paraffinic waxes of 30:70 to 80:20, preferably 40:60 to 75:25,more preferably 50:50 to 70:30. The weight ratio of n- to isoparaffinicwaxes can be determined by means of gas chromatography to ASTM D 5442.

The wax, preferably paraffinic wax, may have a molecular weight M_(w) of250-800 g/mol, preferably 350-700 g/mol, more preferably 400-600 g/mol.The molecular weight M_(w) of the wax can be determined by means of gaschromatography to ASTM D 5442.

The mercaptosilanes of the general formula I can be compounds where R¹is an alkyl polyether group —O—(R⁵—O)_(m)—R⁶, where R⁵ is identical ordifferent and is a branched or unbranched, saturated or unsaturated,aliphatic divalent C1-C30 hydrocarbon group, m is on average from 1 to30, and R⁶ is composed of at least 11 C atoms and is an unsubstituted orsubstituted, branched or unbranched monovalent alkyl, alkenyl, aryl oraralkyl group,

R² is identical and is a C1-C12-alkyl or R⁷O group, where R⁷ is H,ethyl, propyl, C9-C30 branched or unbranched monovalent alkyl, alkenyl,aryl, or aralkyl group or (R⁸)₃Si group, where R⁸ is C1-C30 branched orunbranched alkyl or alkenyl group,

R³ is a branched or unbranched, saturated or unsaturated, aliphatic,aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon groupand

R⁴ is H, CN or (C═O)—R⁹, where R⁹ is a branched or unbranched, saturatedor unsaturated, aliphatic, aromatic or mixed aliphatic/aromaticmonovalent C1-C30 hydrocarbon group.

The mercaptosilanes of the general formula E can be compounds where R¹is

—O—(C₂H₄—O)₅—C₁₁H₂₃, —O—(C₂H₄—O)₅—C₁₂H₂₅, —O—(C₂H₄—O)₅—C₁₃H₂₇,—O—(C₂H₄—O)₅—C₁₄H₂₉, —O—(C₂H₄—O)₅—C₁₅H₃₁, —O—(C₂H₄—O)₃—C₁₃H₂₇,—O—(C₂H₄—O)₄—C₁₃H₂₇, —O—(C₂H₄—O)₆—C₁₃H₂₇, —O—(C₂H₄—O)₇—C₁₃H₂₇—,—O—(CH₂CH₂—O)₅—(CH₂)₁₀CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₁CH₃,—O—(CH₂CH₂—O)₅—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₅—(CH₂))₁₃CH₃,—O—(CH₂CH₂—O)₅—(CH₂)₁₄CH₃, —O—(CH₂CH₂—O)₃—(CH₂)₁₂CH₃,—O—(CH₂CH₂—O)₄—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₆—(CH₂)₁₂CH₃,—O—(CH₂CH₂—O)₂—(CH₂)₁₂CH₃,

R² is different and is an R¹-, C1-C12-alkyl or R⁷O group, where R⁷ is H,methyl, ethyl, propyl, C9-C30 branched or unbranched monovalent alkyl,alkenyl, aryl, aralkyl group or (R⁸)₃Si group, where R⁸ is C1-C30branched or unbranched alkyl or alkenyl group,R³ is a branched or unbranched, saturated or unsaturated, aliphatic,aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon groupandR⁴ is H, CN or (C═O)—R⁹, where R⁹ is a branched or unbranched, saturatedor unsaturated, aliphatic, aromatic or mixed aliphatic/aromaticmonovalent C1-C30 hydrocarbon group.

The mercaptosilanes of the general formula I can be compounds where R¹is

—O—(C₂H₄—O)₅—C₁₁H₂₃, —O—(C₂H₄—O)₅—C₁₂H₂₅, —O—(C₂H₄—O)₅—C₁₃H₂₇,—O—(C₂H₄—O)₅—C₁₄H₂₉, —O—(C₂H₄—O)₅—C₁₅H₃₁, —O—(C₂H₄—O)₃—C₁₃H₂₇,—O—(C₂H₄—O)₄—C₁₃H₂₇, —O—(C₂H₄—O)₆—C₁₃H₂₇, —O—(C₂H₄—O)₇—C₁₃H₂₇,—O—(CH₂CH₂—O)₅—(CH₂)₁₀CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₁CH₃,—O—(CH₂CH₂—O)₅—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₃CH₃,—O—(CH₂CH₂—O)₅—(CH₂)₁₄CH₃, —O—(CH₂CH₂—O)₃—(CH₂)₁₂CH₃,—O—(CH₂CH₂—O)₄—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₆—(CH₂)₁₂CH₃,—O—(CH₂CH₂—O)₇—(CH₂)₁₂CH₃,

R² is an R¹ group,R³ is a branched or unbranched, saturated or unsaturated, aliphatic,aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon groupandR⁴ is H, CN or (C═O)—R⁹, where R⁹ is a branched or unbranched, saturatedor unsaturated, aliphatic, aromatic or mixed aliphatic/aromaticmonovalent C1-C30 hydrocarbon group.

Preferred compounds of the formula I where R⁴=H can be:

[(C₁₁H₂₃O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[C₁₂H₂₅O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃](EtO)₂—Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₃(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₃(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₃(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₃(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄]₃(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄]₃(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄]₃(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH, where R⁶ can be branchedor unbranched.

Preferred compounds of the formula I where R⁴=CN can be:

[(C₁₁H₂₃O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₂ (EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₂ (EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₂ (EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₃ (EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₃ (EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₃ (EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₃(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₃(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₃ (EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₃(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₃(EtO)Si(CH₂)₃SCN, where R⁶ can be branched orunbranched.

Preferred compounds of the formula I where R⁴=—C(═O)—R⁹ and R⁹=branchedor unbranched —C₅H₁₁, —C₆H₃₃, —C₇H₁₅, —C₈H₁₇, C₉H₁₉, —C₁₀H₂₁, —C₁₁H₂₃,—C₁₂H₂₅, —C₁₃H₂₇, —C₁₄H₂₉, —C₁₅H₃₁, —C₁₆H₃₃, —C₁₇H₃₅ and —C₆H₅(phenyl)can be:

[(C₁₁H₂₃O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₃Si(CH₂)₃—C(═O)—R⁹,

R⁶ can preferably be C₁₂ to C₁₇, very particularly preferably C₁₂ toC₁₆, extremely preferably C₁₂ to C₁₄, unsubstituted or substituted,branched or unbranched monovalent alkyl.

R⁶ can be a —C₁₁H₂₃, —C₁₂H₂₅, —C₁₃H₂₇, —C₁₄H₂₉, —C₁₅H₃₁, —C₁₆H₃₃ or—C₁₇H₃₅ alkyl group.

R⁶ can preferably be C₁₁ to C₃₅, particularly preferably C₁₁ to C₃₀,very particularly preferably C₁₂ to C₃₀, extremely preferably C₁₃ toC₂₀, unsubstituted or substituted, branched or unbranched monovalentalkenyl.

R⁶ can preferably be C₁₁ to C₁₄ and/or C₁₆ to C₃₀, very particularlypreferably C₁₁ to C₁₄ and/or C₁₆ to C₂₅, extremely preferably C₁₂ to C₁₄and/or C₁₆ to C₂₀, unsubstituted or substituted, branched or unbranchedmonovalent aralkyl.

R⁶ as alkenyl can be C₁₁H₂₁, —C₁₂H₂₃, —C₁₃H₂₅, —C₁₄H₂₇, —C₁₅H₂₉, —C₁₆H₃₁or —C₁₇H₃₃.

R¹ can be an alkoxylated castor oil (e.g. CAS 61791-12-6).

R¹ can be an alkoxylated oleylamine (e.g. CAS 26635-93-8).

The polyether group (R⁵O)_(m) can comprise random units of ethylene andpropylene oxide or polyether blocks made of polyethylene oxide andpolypropylene oxide.

The polyether group (R⁵—O)_(m) can preferably be:

(—O—CH₂—CH₂—)_(a),

(—O—CH(CH₃)—CH₂—)_(a),

(—O—CH₂—CH(CH₃)−)_(a),

(—O—CH₂—CH₂—)_(a)(—O—CH(CH₃)—CH₂—)_(a),

(—O—CH₂—CH₂—)(—O—CH(CH₃)—CH₂—)_(a),

(—O—CH₂—CH₂—)_(a)(—O—CH₂—CH(CH₃)—)_(a),

(—O—CH₂—CH₂—)(—O—CH₂—CH(CH₃)—)_(a),

(—O—CH(CH₃)—CH₂—)_(a)(—O—CH₂—CH(CH₃)—),

(—O—CH(CH₃)—CH₂—)(—O—CH₂—CH(CH₃)—)_(a),

(—O—CH₂—CH₂—)_(a)(—O—CH(CH₃)—CH₂—)_(b)(—O—CH₂—CH(CH₃)—)_(a) or acombination of these,

where a, b and c are mutually independent and

a is from 1 to 50, preferably from 2 to 30, particularly preferably from3 to 20, very particularly preferably from 4 to 15, extremely preferablyfrom 5 to 12,

b is from 1 to 50, preferably from 2 to 30, particularly preferably from3 to 20, very particularly preferably from 4 to 15, extremely preferablyfrom 5 to 12 and

c is from 1 to 50, preferably from 2 to 30, particularly preferably from3 to 20, very particularly preferably from 4 to 15, extremely preferablyfrom 5 to 12.

The indices a, b and c are integers and denote the number of repeatingunits.

When R⁴ is —H, —CN or —C(═O)—R⁹, the group (R⁵—O)_(m) can preferablycomprise ethylene oxide units (CH₂—CH₂—O)_(a) or propylene oxide units(CH(CH₃)—CH₂—O)_(a) or (CH₂—CH(CH₃)—O)_(a).

When R⁴ is —H, —CN or —C(═O)—R⁹, the group (R⁵—O)_(m) can preferablycomprise the following randomly distributed or in blocks: ethylene oxideunits (CH₂—CH₂—O), or propylene oxide units (CH(CH₃)—CH₂—O) or(CH₂—CH(CH₃)—O)_(a).

When R⁴ is —H, the alkyl polyether group (R⁵—O)_(m) can preferablycomprise the following randomly distributed or in blocks: ethylene oxideunits (CH₂—CH₂—O)_(a) or propylene oxide units (CH(CH₃)—CH₂—O)_(a) or(CH₂—CH(CH₃)—O)_(a).

When R⁴ is —H, the group (R⁵—O)_(m) can preferably comprise propyleneoxide units (CH(CH₃)—CH₂—O), or (CH₂—CH(CH₃)—O)_(a).

When R⁴ is —H, —CN or —C(C═O)—R⁹, the alkyl polyether groupO—(R⁵—O)_(m)—R⁶ can be:

O—(CH₂—CH₂O)₂—C₁₁—H₂₃, O—(CH₂—CH₂O)₃—C₁₁H₂₃, O—(CH₂—CH₂O)₄—C₁₁H₂₃,O—(CH₂—CH₂O)₅—C₁₁H₂₃, O—(CH₂—CH₂O)₆—C₁₁H₂₃, O—(CH₂—CH₂O)₇—C₁₁H₂₃,

O—(CH(CH₃)—CH₂O)₂—C₁₁H₂₃, O—(CH(CH₃)—CH₂O)₃—C₁₁H₂₃,O—(CH(CH₃)—CH₂O)₄—C₁₁H₂₃, O—(CH(CH₃)—CH₂O)₅—C₁₁H₂₃,O—(CH(CH₃)—CH₂O)₆—C₁₁H₂₃, O—(CH(CH₃)—CH₂O)₇C₁₁H₂₃,

O—(CH₂—CH₂O)₂—C₁₂H₂₅, O—(CH₂—CH₂O)₃—C₁₂H₂₅, O—(CH₂—CH₂O)₄—C₁₂H₂₅,O—(CH₂—CH₂O)₅—C₁₂H₂₅, O—(CH₂—CH₂O)₆—C₁₂H₂₅, O—(CH₂—CH₂O)—C₁₂H₂₅,

O—(CH(CH₃)—CH₂O)₂—C₁₂H₂₅, O—(CH(CH₃)—CH₂O)₃—C₁₂H₂₅,O—(CH(CH₃)—CH₂O)₄—C₁₂H₂₅, O—(CH(CH₃)—CH₂O)₅—C₁₂H₂₅,O—(CH(CH₃)—CH₂O)₆—C₁₂H₂₅, O—(CH(CH₃)—CH₃O)₇—C₁₂H₂₅,

O—(CH₂—CH₂O)₂—C₁₃H₂₇, O—(CH₂—CH₂O)₃—C₁₃H₂₇, O—(CH₂—CH₂O)₄—C₁₃H₂₇,O—(CH₂—CH₂O)₅—C₁₃H₂₇, O—(CH₂—CH₂O)₆—C₁₃H₂₇, O—(CH₂—CH₂O)₇—C₁₃H₂₇,

O—(CH(CH₃)—CH₂O)₂—C₁₃H₂₇, O—(CH(CH₃)—CH₂O)₃—C₁₃H₂₇,O—(CH(CH₃)—CH₂O)₄—C₁₃H₂₇—, O—(CH(CH₃)—CH₂O)₅—C₁₃H₂₇,O—(CH(CH₃)—CH₂O)₆—C₁₃H₂₇, O—(CH(CH₃)—CH₂O)₇—C₁₃H₂₇,

O—(CH₂—CH₂O)₂—C₁₄H₂₉, O—(CH₂—CH₂O)₃—C₁₄H₂₉), O—(CH₂—CH₂O)₄—C₁₄H₂₉,O—(CH₂—CH₂O)₅—C₁₄H₂₉, O—(CH₂—CH₂O)₃—C₁₄H₂₉, O—(CH₂—CH₂O)₇—C₁₄H₂₉,

O—(CH(CH₃)—CH₂O)₂—C₁₄H₂₉, O—(CH(CH₃)—CH₂O)₃—C₁₄H₂₉,O—(CH(CH₃)—CH₂O)₄—C₁₄H₂₉, O—(CH(CH₃)—CH₂O)₅—C₁₄H₂₉,O—(CH(CH₃)—CH₂O)₆—C₁₄H₂₉, O—(CH(CH₃)—CH₂O)₇—C₁₄H₂₉,

O—(CH₂—CH₂O)₂—C₁₅H₃₁, O—(CH₂—CH₂O)₃—C₁₅H₃₁, O—(CH₂—CH₂O)₄—C₁₅H₃₁,O—(CH₂—CH₂O)₅—C₁₅H₃₁, O—(CH₂—CH₂O)₆—C₁₅H₃₁, O—(CH₂—CH₂O)₇—C₁₅H₃₁,

O—(CH(CH₃)—CH₂O)₂—C₁₅H₃₁, O—(CH(CH₃)—CH₂O)₃—C₁₅H₃₁,O—(CH(CH₃)—CH₂O)₄—C₁₅H₃₁, O—(CH(CH₃)—CH₂O)₅—C₁₅H₃₁,O—(CH(CH₃)—CH₂O)₆—C₁₅H₃₁, O—(CH(CH₃)—CH₂O)₇—C₁₅H₃₁,

O—(CH₂—CH₂O)₂—C₁₆H₃₃, O—(CH₂—CH₂O)₃—C₁₆H₃₃, O—(CH₂—CH₂O)₄—C₁₆H₃₃,O—(CH₂—CH₂O)₅—C₁₆H₃₃, O—(CH₂—CH₂O)₆—C₁₆H₃₃, O—(CH₂—CH₂O)₇—C₁₆H₃₃,

O—(CH(CH₃)—CH₂O)₂—C₁₆H₃₃, O—(CH(CH₃)—CH₂O)₃—C₁₆H₃₃,O—(CH(CH₃)—CH₂O)₄—C₁₆H₃₃, O—(CH(CH₃)—CH₂O)₅—C₁₆H₃₃,O—(CH(CH₃)—CH₂O)₆—C₁₆H₃₃, O—(CH(CH₃)—CH₂O)₇—C₁₆H₃₃,

O—(CH₂—CH₂O)₂—C₁₇H₃₅, O—(CH₂—CH₂O)₃—C₁₇H₃₅, O—(CH₂—CH₂O)₄C₁₇H₃₅,O—(CH₂—CH₂O)₅—C₁₇H₃₅, O—(CH₂—CH₂O)₆—C₁₇H₃₅, O—(CH₂—CH₂O)₇—C₁₇H₃₅,

O—(CH(CH₃)—CH₂O)₂—C₁₇H₃₅, O—(CH(CH₃)—CH₂O)₃—C₁₇H₃₅,O—(CH(CH₃)—CH₂O)₄—C₁₇H₃₅, O—(CH(CH₃)—CH₂O)₅—C₁₇H₃₅,O—(CH(CH₃)—CH₂O)₆—C₁₇H₃₅ or O—(CH(CH₃)—CH₂O)₇—C₁₇H₃₅.

The group R⁵ can have substitution. The group R⁶ can be

R¹ can be —O—(C₂H₄—O)₅—C₁₁H₂₃, —O—(C₂H₄—O)₅—C₁₂H₂₅, —O—(C₂H₄—O)₅—C₁₃H₂₇,—O—(C₂H₄—O)₅—C₁₄H₂₉, —O—(C₂H₄—O)₅—C₁₅H₃₁, —O—(C₂H₄—O)₃—C₁₃H₂₇,—O—(C₂H₄—O)₄—C₁₃H₂₇, —O—(C₂H₄—O)₆—C₁₃H₂₇, —O—(C₂H₄—O)₇—C₁₃H₂₇,—O—(CH₂CH₂—O)₅—(CH₂)₁₀CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₁CH₃,—O—(CH₂CH₂O)₅—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₃CH₃,—O—(CH₂CH₂—O)₅—(CH₂)₁₄CH₃, —O—(CH₂CH₂—O)₃—(CH₂)₁₂CH₃,—O—(CH₂CH₂—O)₄—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₆—(CH₂)₁₂CH₃,—O—(CH₂CH₂—O)₇—(CH₂)₁₂CH₃,

The average branching number of the carbon chain R⁶ can be from 1 to 5,preferably from 1.2 to 4. The average branching number is defined hereas the number of CH₃ groups-1.

R³ can be CH₂, CH₂CH₂, CH₂CH₂CH₂, CH₂CH₂CH₂CH₂, CH(CH₃), CH₂CH(CH₃),CH(CH₃)CH₂, C(CH₃)₂, CH(C₂H₅), CH₂CH₂CH(CH₃), CH₂CH(CH₃)CH₂

or

The mercaptosilane-wax mixture can comprise a mixture of differentmercaptosilanes of the general formula I and optionally of condensatesof these.

The mixture of different mercaptosilanes of the general formula I cancomprise mercaptosilanes of the general formula I having various mvalues.

The mixture of different mercaptosilanes of the general formula I cancomprise mercaptosilanes of the general formula I having various R⁶groups. The R⁶ groups here can have different C-atom-chain lengths.

The mixture of different mercaptosilanes of the general formula I cancomprise different mercaptosilanes of the general formula I havingvarious R and R² groups where the R¹ and R² groups are composed ofalkoxy and alkyl polyether groups.

The mixture of different mercaptosilanes of the general formula I cancomprise different mercaptosilanes of the general formula I havingdifferent R².

The mixture of different mercaptosilanes of the general formula I cancomprise different mercaptosilanes of the general formula I havingvarious R¹ and R² groups where the R¹ groups are composed of alkylpolyether groups and the R² groups are composed of ethoxy groups and R⁶has an alkyl-chain length of 13 C atoms, R⁵ is ethylene and m is onaverage 5.

The mixture of different mercaptosilanes of the general formula I cancomprise different mercaptosilanes of the general formula I where R² isidentical or different and is an ethoxy or alkyl polyether group (R¹),R⁶ has an alkyl-chain length of 13 C atoms, R⁵ is ethylene and m is onaverage 5, and R² is different.

The mixture of different mercaptosilanes of the general formula I cancomprise different mercaptosilanes of the general formula I where R¹ andR² are alkoxy and alkyl polyether groups and R⁶ is composed of differentC-atom-chain lengths.

The mixture of different mercaptosilanes of the general formula I cancomprise different mercaptosilanes of the general formula I where R² isidentical or different and is an alkoxy or alkyl polyether group (R¹),and R² in the mixture is different, and R⁶ is composed of differentC-atom-chain lengths.

The mixture of different mercaptosilanes of the general formula I canpreferably comprise

and optionally products of the hydrolysis and/or condensation of theabovementioned compounds.

From the mercaptosilanes of the formula I it is easily possible viawater addition and optionally additive addition to form condensates,i.e. oligo- and polysiloxanes.

These oligomeric or polymeric siloxanes of the compounds of the formulaI can be used as coupling reagents for the same applications as themonomeric compounds of the formula I.

The mercaptosilane compounds can also take the form of mixture of theoligomeric or polymeric siloxanes of mercaptosilanes of the generalformula I or take the form of mixtures of mercaptosilanes of the generalformula I with mixtures of the oligomeric or polymeric siloxanes ofmercaptosilanes of the general formula I.

The invention further provides a process for the production of theplastics-covered mercaptosilane-wax mixtures of the invention, the saidprocess being characterized in that in a first step a mercaptosilane-waxmixture is obtained through mixing of at least one mercaptosilane of thegeneral formula I with at least one wax, preferably a paraffinic wax,particularly preferably a mixture of different paraffinic waxes, withparticular preference a mixture of n and iso paraffinic waxes withcongealing point from 30 to 160° C., preferably from 40 to 130° C.,particularly preferably from 60 to 80° C., and in a second step themercaptosilane-wax mixture from the first step is charged to a plasticssachet, where the plastic of the sachet is selected from the group ofpolypropylene, polyethylene, preferably LDPE, ethylene-vinyl acetatecopolymer and mixtures of the abovementioned plastics with melting pointfrom 70 to 170° C., preferably from 85 to 140° C., particularlypreferably from 100 to 120° C., and the plastics sachet is sealed.

The plastics sachet can comprise >90% by weight of plastic, preferably≥95% by weight, particularly preferably >97% by weight. The plasticssachet can be composed of polypropylene, polyethylene, preferably LDPE,ethylene-vinyl acetate copolymer or a mixture of the abovementionedplastics.

The process of the invention can be carried out continuously orbatchwise.

The ratio by weight of mercaptosilane of the general formula I to waxcan be from 10:90 to 95:5, preferably from 80:20 to 85:15.

In the first step of the process of the invention the mercaptosilane-waxmixture can be produced at temperatures of from 30 to 160° C.,preferably from 40 to 130° C., particularly preferably from 60 to 80° C.

In the second step of the process of the invention themercaptosilane-wax mixture can be charged to the plastics sachet at atemperature of from 30 to 160° C., preferably from 40 to 130° C.,particularly preferably from 60 to 80° C.

For the avoidance of condensation reactions the production of themercaptosilane-wax mixture and/or the charging of material to theplastics sachets can take place in an anhydrous environment,particularly preferably in an inert gas atmosphere.

The process of the invention can be carried out at atmospheric pressure.

A temperature-controllable kneading, stirring or mixing assembly can beused to mix the mercaptosilane of the general formula I with the wax inthe first step of the process of the invention. Use of this kneading,stirring or mixing assembly can achieve uniform motion of, and mixingof, the product.

A parameter frequently used for the classification of commerciallyavailable mixers here is the Froude number (Fr), which gives the ratioof centrifugal acceleration to gravitational acceleration.

It is possible to use not only low-speed mixers where Fr<1, for exampletumbling mixers or displacement mixers, but also high-speed mixers whereFr>1, for example impeller mixers, and also centrifugal mixers whereFr>>1. Examples of a low-speed displacement mixer that can be used aredrum mixers (for example from Engelsmann) and twin-shaft mixers (forexample from Gericke or Forberg). Examples of high-speed mixers that canbe used for the region where Fr>1 are ploughshare mixers (for examplefrom Lödige) and vertical twin-shaft mixers (for example from Amixon).In the region where Fr>>1 it is possible to use centrifugal or intensivemixers (for example from Eirich or Mixaco).

The temperature during the mixing process here can be above thecongealing point of the wax. The wax can be introduced in liquid forminto the mixer, for example by means of nozzles, after prior melting.

The plastics sachets can be sealed by welding, heat sealing, coldsealing, ultrasound sealing or sealing with closure clip (e.g. made ofplastic).

The plastics-covered mercaptosilane-wax mixture of the invention canalso comprise fillers, preferably silicas or carbon black, and alsoother rubber auxiliaries, for example reaction accelerators,antioxidants, heat stabilizers, light stabilizers, antiozonants,processing aids, plasticizers, tackifiers, blowing agents, dyes,pigments, waxes, extenders, organic acids, retarders, metal oxides, andalso activators, for example triethanolamine, polyethylene glycol,and/or hexanetriol. These compounds are known in the rubber industry.Specifically these can by way of example be—where the followingsubstances do not restrict the invention or the information providedabove: substituted phenols, aromatic amines, e.g. phenylenediaminederivatives, sterically hindered amines, e.g.2,2,4-trimethyl-1,2-dihydroquinoline, metal salts, silanes, long-chaincarboxylic acids, fatty acids, zinc salts, zinc soaps or resins.

The plastics-covered mercaptosilane-wax mixture of the invention can beused as coupling agent between inorganic materials, for example glassfibres, metals, oxidic fillers, or silicas, and organic polymers, forexample thermosets, thermoplastics or elastomers, or as crosslinkingagent and surface modifier. The plastics-covered mercaptosilane-waxmixture of the invention can be used as coupling reagent in rubbermixtures, for example tyre treads.

The invention further provides a rubber mixture comprising

(A) at least one rubber,

(B) at least one filler, preferably precipitated silica, and

(C) at least one plastics-covered mercaptosilane-wax mixture of theinvention.

Rubber used can be natural rubber and/or synthetic rubbers. Preferredsynthetic rubbers are described, for example, in W. Hofmann,Kautschuktechnologie [Rubber Technology], Genter Verlag, Stuttgart 1980.They can be inter alia

-   -   polybutadiene (BR);    -   polyisoprene (IR)        styrene/butadiene copolymers, for example emulsion SBR (E-SBR)        or solution SBR (S-SBR), preferably having styrene contents of        from 1 to 60% by weight, particularly from 5 to 50% by weight        (SBR),    -   chloroprene (CR);    -   isobutylene/isoprene copolymers (IIR)    -   butadiene/acrylonitrile copolymers having acrylonitrile contents        of 5 to 60%, preferably 10 to 50%, by weight (NBR)    -   partly hydrogenated or fully hydrogenated NBR rubber (HNBR);    -   ethylene/propylene/diene copolymers (EPDM);    -   abovementioned rubbers which also have functional groups, e.g.        carboxy, silanol, amino, mercapto or epoxy groups, for example        epoxidized NR, carboxy-functionalized NBR or silanol (—SiOH)— or        siloxy (—Si—OR)-functionalized SBR,        or else a mixture of these rubbers.

In a preferred embodiment, the rubbers can be sulphur-vulcanizable.Production of car tyre treads can in particular use anionicallypolymerized S-SBRs (solution SBRs) with glass transition temperatureabove −50° C., or else a mixture of these with diene rubbers. It isparticularly preferably possible to use S-SBR rubbers whose butadieneportion has more than 20% by weight vinyl fraction. It is veryparticularly preferably possible to use S-SBR rubbers whose butadieneportion has more than 50% by weight vinyl fraction.

It is preferably possible to use mixtures of the abovementioned rubberswhich have more than 50% by weight, particularly more than 60% byweight, S-SBR content.

The following fillers can be used as fillers for the rubber mixture ofthe invention:

-   -   carbon blacks: The carbon blacks to be used here are those        produced by the lamp-black, furnace, gas-black or thermal        process, having BET surface areas of from 20 to 200 m²/g. The        carbon blacks can optionally also comprise heteroatoms, for        example Si.    -   Amorphous silicas, produced for example by precipitation from        solutions of silicates or by flame hydrolysis of silicon halides        with specific surface areas of from 5 to 1000 m²/g, preferably        from 20 to 400 m²/g (BET surface area) and with primary particle        sizes of from 10 to 400 nm. The silicas may optionally also take        the form of mixed oxides with other metal oxides, for example Al        oxides, Mg oxides, Ca oxides, Ba oxides, Zn oxides and titanium        oxides.    -   Synthetic silicates, for example aluminium silicate, alkaline        earth metal silicates such as magnesium silicate or calcium        silicate, having BET surface areas of from 20 to 400 m²/g and        primary particle diameters of from 10 to 400 nm.    -   Synthetic or natural aluminium oxides and, respectively,        aluminium hydroxides.    -   Natural silicates, for example kaolin and other naturally        occurring silicas.    -   Glass fibres and glass-fibre products (mats, strands) or glass        microbeads.

It is preferably possible to use quantities of from 5 to 150 parts byweight, based in each case on 100 parts of rubber, of amorphous silicasproduced by precipitation from solutions of silicates, having BETsurface areas of from 20 to 400 m²/g, particularly from 100 m²/g to 250m²/g.

The fillers mentioned can be used alone or in a mixture.

The rubber mixture can comprise from 5 to 150 parts by weight of filler(B) and from 0.1 to 35 parts by weight, preferably from 2 to 20 parts byweight, particularly preferably from 5 to 20 parts by weight, ofplastics-covered mercaptosilane-wax mixture (C) of the invention, wherethe parts by weight are based on 100 parts by weight of rubber.

The rubber mixture can also comprise silicone oil and/or alkylsilane.

The rubber mixture of the invention can comprise other known rubberauxiliaries, e.g. crosslinking agents, vulcanization accelerators,reaction accelerators, reaction retarders, antioxidants, stabilizers,processing aids, plasticizers, waxes or metal oxides, and alsooptionally activators such as triethanolamine, polyethylene glycol orhexanetriol.

The quantities used of the rubber auxiliaries can be conventional,depending inter alia on the intended use. Conventional quantities can byway of example be amounts of from 0.1 to 50% by weight, based on rubber.

Sulphur or organic sulphur donors can be used as crosslinking agents.

The rubber mixture of the invention can comprise other vulcanizationaccelerators. Examples of suitable vulcanization accelerators that canbe used are mercaptobenzothiazoles, suiphenamides, guanidines,dithiocarbamates, thioureas, thiocarbonates, and also zinc salts ofthese, for example zinc dibutyldithiocarbamate.

The rubber mixture of the invention can preferably also comprise

(D) a thiuram sulphide accelerator and/or carbamate accelerator and/orthe corresponding zinc salts,

(E) a nitrogen-containing co-activator,

(F) optionally other rubber auxiliaries and

(G) optionally other accelerators,

where the ratio by weight of accelerator (D) to nitrogen-containingco-activator (E) is equal to or greater than 1.

The rubber mixture of the invention can comprise at least 0.25 part byweight, based on 100 parts by weight of rubber, of (D)tetrabenzylthiuram disulphide or tetramethylthiuram disulphide, at most0.25 part by weight, based on 100 parts by weight of rubber, of (E)diphenylguanidine, and more parts by weight than (D) of (G) cyclohexyl-or dicyclohexylsulphenamide.

It is preferably possible to use sulphenamides together with guanidinesand thiurams, particularly cyclohexylsulphenamide ordicylohexylsulphenamide together with diphenylguanidine andtetrabenzylthiuram disulphide or tetramethylthiuram disulphide.

Quantities that can be used of the vulcanization accelerators andsulphur are from 0.1 to 10% by weight, preferably from 0.1 to 5% byweight, based on the rubber used. It is particularly preferably possibleto use quantities of from 1 to 4% by weight of sulphur andsulphenamides, quantities of from 0.2 to 1% by weight of thiurams andquantities of from 0 to 0.5% by weight of guanidines.

The rubber mixtures of the invention can be produced by mixing, in amixing assembly, at least one rubber (A), at least one filler (B), atleast one plastics-covered mercaptosilane-wax mixture (C) of theinvention, and optionally other rubber auxiliaries.

The mixing of the rubbers with the filler, optionally rubberauxiliaries, and the plastics-covered mercaptosilane-wax mixture of theinvention can be carried out in/on conventional mixing assemblies, forexample rolls, internal mixers and mixing extruders. Rubber mixtures ofthis type can usually be produced in internal mixers by first, in one ormore successive thermomechanical mixing stages at from 100 to 170° C.,mixing to incorporate the rubbers, the filler, the plastics-coveredmercaptosilane-wax mixture of the invention and the rubber auxiliaries.The addition sequence and the juncture of addition of the individualcomponents here can have a decisive effect on the properties obtainedfrom the mixture. It is usually possible to admix the crosslinkingchemicals with the resultant rubber mixture in an internal mixer or on aroll at from 40 to 110° C. and to process the mixture to give what isknown as the crude mixture for the subsequent steps of processing, forexample shaping and vulcanization.

The rubber mixture of the invention can be vulcanized at temperatures of80 to 200° C., preferably 110 to 180° C., optionally under a pressure of10 to 200 bar.

The rubber mixture of the invention can be used for the production ofmouldings, for example for the production of pneumatic and other tyres,tyre treads, cable sheathing, hoses, drive belts, conveyor belts, rollcoverings, shoe soles, sealing elements, for example sealing rings, anddamping elements.

Mouldings can be produced by vulcanization from the rubber mixtures ofthe invention.

The plastics-covered mercaptosilane-wax mixture of the invention has theadvantage that the monomer content of the mercaptosilane undergoes nosignificant change even during prolonged storage.

Another advantage is good processability and handling properties.

EXAMPLES Example 1: (Shelf Life of Plastics Sachet with and without Wax)Comparative Example 1

1. Flat sachet made of unmodified LDPE, dimensions: 170 mm×300 mm (L×W),thickness: 100 μm from neoLab Migge Laborbedarf-Vertriebs GmbH, Germany.

2. VP Si 363 silane from Evonik Industries AG.

500 g of VP Si 363 is charged under inert conditions (MB 150-GIIglovebox from MBraun Inertgas-Systeme GmbH, Germany) to flat polymersachets, and commercially available film-welding equipment fromBraukmann GmbH, Germany (Caso® VC10 Vakuumierer) is used for the weldingprocess.

Inventive Example 1

1. Flat sachet made of unmodified LDPE, dimensions: 170 mm×300 mm (L×W),thickness: 100 μm from neoLab Migge Laborbedarf-Vertriebs GnmbH,Germany.

2. Protektor G3108 from Paramelt (composition: mixture of refinedhydrocarbon waxes, congealing point ≈57° C., relative density ≈from 0.89to 0.96 g/cm³ (20° C.), viscosity ≈4 mPas (100° C.).

3. VP Si 363 silane from Evonik Industries AG.

The mercaptosilane-wax mixture is produced by melting Protektor G3108 inthe presence of VP Si 363 in a ratio by weight of 1:5 in a 1000 mL glassbeaker on a hotplate with stirrer motor at 65° C. under inert conditions(glovebox from MBraun Inertgas-Systeme GmbH, Germany (MB 150-GII)). 500g of the liquid, homogeneous, warm physical mixture of Protektor G3108and VP Si 363 is then charged under inert conditions (glovebox fromMBraun Inertgas-Systeme GmbH, Germany (MB 150-GII)) to flat polymersachets; commercially available film-welding equipment from BraukmannGmbH, Germany (Caso® VC10 Vakuumierer) is used for the welding process,and the material is allowed to cool at room temperature for hardening.

The samples are stored uncovered in aluminium dishes for 3 months at 23°C. and 50% humidity.

The shelf life of the samples is evaluated on the basis of the remainingcontent of VP Si 363 monomer in comparison with oligomeric structures byusing ²⁹Si NMR measurements. The results are shown in Table 1.

The ²⁹Si NMR measurements are made in a 500 MHz “Bruker Avance 500” fromBruker with nitrogen-cooled cryohead (about 2000 scans). For preparationof the samples of the silane/wax mixture, about 0.5 g of the sample isadded to a Brand culture tube with screw closure, from 3 to 4 mL ofCDCl₃ and Cr(acac)₃ are added, and the mixture is treated three timesfor 15 minutes in a Panasonic 470/H Ultrasound bath. It is thencentrifuged and also filtered. An NMR spectrum of the solution is thenrecorded.

TABLE 1 Monomer content [mol %] Monomer content prior to [mol %] storageafter storage Comparative Example 1 99 73 Inventive Example 1: 97 96

Ageing effects are greatly suppressed by the combination of LDPE filmand Protektor wax when comparison is made with the wax-free ComparativeExample 1.

Example 2: (Shelf Life with Wax with and without Film; Comparison ofFilm Thicknesses) Comparative Example 2

Materials Used:

1. FLB flat sachet from Polymersynthesewerk GmbH, melting point: 104°C., thickness: 60 μm.

Polymer: Exxonmobil LD 362 BR produced by A. Schulman GmbH, based on anLDPE/EVA copolymer (vinyl acetate content: 4.5% by weight, density:0.928 g/cm³, melt flow rate (190° C./2.16 kg): 2.0 g/10 min).

2. Protektor G3108 from Paramelt (composition: mixture of refinedhydrocarbon waxes, congealing point ≈57° C., relative density ≈0.89-0.96g/cm³ (20° C.), viscosity ≈4 mPas (100° C.).

3. VP Si 363 silane from Evonik Industries AG.

The mixtures are produced by melting Protektor G3108 and VP Si 363together in a ratio by weight of 1:5 in a 1000 mL glass beaker on ahotplate with stirrer motor at 65° C. under inert conditions (gloveboxfrom MBraun Inertgas-Systeme GmbH, Germany (MB 150-GII)). 500 g of theliquid, homogeneous, warm physical mixture of Protektor G3108 and VP Si363 is then charged under inert conditions (glovebox from MBraunInertgas-Systeme GmbH, Germany (MB 150-GII)) to flat polymer sachets;commercially available film-welding equipment from Braukmann GmbH,Germany (Caso® VC10 Vakuumierer) is used for the welding process, andthe material is allowed to cool at room temperature for hardening. Thesachet is removed prior to the storage study.

Comparative Example 3

Materials Used:

1. FLB flat sachet from Polymersynthesewerk GmbH, melting point: 104°C., thickness: 60 μm

Polymer: Exxonmobil LD 362 BR produced by A. Schulman GmbH, based on anLDPE/EVA copolymer (vinyl acetate content: 4.5% by weight, density:0.928 g/cm³, melt flow rate (190° C./2.16 kg): 2.0 g/10 min)

2. Protektor G3108 from Paramelt (composition: mixture of refinedhydrocarbon waxes, congealing point ≈57° C., relative density ≈0.89-0.96g/cm³ (20° C.), viscosity ≈4 mPas (100° C.).

3. VP Si 363 silane from Evonik Industries AG.

The mixtures are produced by melting Protektor G3108 and VP Si 363together in a ratio by weight of 1:5 in a 1000 mL glass beaker on ahotplate with stirrer motor at 65° C. under inert conditions (gloveboxfrom MBraun Inertgas-Systeme GmbH, Germany (MB 150-GII)). 500 g of theliquid, homogeneous, warm physical mixture of Protektor G3108 and VP Si363 is then charged under inert conditions (glovebox from MBraunInertgas-Systeme GmbH, Germany (MB 150-GII)) to flat polymer sachets;commercially available film-welding equipment from Braukmann GmbH,Germany (Caso® VC10 Vakuumierer) is used for the welding process, andthe material is allowed to cool at room temperature for hardening.

Comparative Example 4

Production of the Comparative Example according to the mercaptosilanecarbon-black mixture of the invention in Example 1 of WO2013149790.

Inventive Example 2

Materials Used:

1. FLB flat sachet, Antist/Slip/EVA, from Polymersynthesewerk GmbH,antiblock: 1000 ppm, slip: 750 ppm, heat stabilizers, dimensions: 600mm×900 mm (W×L), melting point: 104° C., weight per metre unfilled: 167g, thickness: 150 μm

Polymer: Exxonmobil LD 362 BR produced by A. Schulman GmbH, based on anLDPE/EVA copolymer (vinyl acetate content: 4.5% by weight, density:0.928 g/cm³, melt flow rate (190° C./2.16 kg): 2.0 g/10 min)

Additive (antistatic agent): Polybatch VLA 55 produced by A. SchulmanGmbH (additive content: 5% by weight, carrier material: PE, melt flowrate: 20 g/10 min, density: 0.96 g/m³, bulk density: 550 g/l, moisturecontent: <1500 ppm.

2. Wax: Protektor G3108 from Paramelt (composition: mixture of refinedhydrocarbon waxes, congealing point ≈57° C., relative density≈0.89-0.96g/cm³ (20° C.), viscosity≈4 mPas (100° C.)).

3. VP Si 363 silane from Evonik Industries AG.

The mixtures are produced by melting Protektor G3108 and VP Si 363together in a ratio by weight of 1:5 in a 1000 mL glass beaker on ahotplate with stirrer motor at 65° C. under inert conditions (gloveboxfrom MBraun Inertgas-Systeme GmbH, Germany (MB 150-GII)). 500 g of theliquid, homogeneous, warm physical mixture of Protektor G3108 and VP Si363 is then charged under inert conditions (glovebox from MBraunInertgas-Systeme GmbH, Germany (MB 150-GII)) to flat polymer sachets;commercially available film-welding equipment from Braukmann GmbH,Germany (Caso® VC10 Vakuumierer) is used for the welding process, andthe material is allowed to cool at room temperature for hardening.

Inventive Example 3

Materials Used:

1. FLB flat sachet, Antist/Slip/EVA, from Polymersynthesewerk GmbH,antiblock: 1000 ppm, slip: 750 ppm, heat stabilizers, dimensions: 600mm×900 mm (W×L), melting point: 104° C., weight per metre unfilled: 167g, thickness: 150 μm

Polymer: Exxonmobil LD 362 BR produced by A. Schulman GmbH, based on anLDPE/EVA copolymer (vinyl acetate content: 4.5% by weight, density:0.928 g/cm, melt flow rate: 2.0 g/10 min)

Additive (antistatic agent): Polybatch VLA 55 produced by A. SchulmanGmbH (additive content: 5% by weight, carrier material: PE, melt flowrate: 20 g/10 min, density: 0.96 g/m³, bulk density: 550 g/l, moisturecontent: <1500 ppm.

2. Wax: Varazon 5998 from Sasol (composition: mixture of paraffin waxesand hydrocarbon waxes from 50 to 100%, coagulation range a from 64 to68° C.).

3. VP Si 363 silane from Evonik Industries AG.

The mixtures are produced by melting Varazon 5998 and VP Si 363 togetherin a ratio by weight of 1:5 in a 1000 mL glass beaker on a hotplate withstirrer motor at 75° C. under inert conditions (glovebox from MBraunInertgas-Systeme GmbH, Germany (MB 150-GII)). 500 g of the liquid,homogeneous, warm physical mixture of Varazon 5998 and VP Si 363 is thencharged under inert conditions (glovebox from MBraun Inertgas-SystemeGmbH, Germany (MB 150-GII)) to flat polymer sachets; commerciallyavailable film-welding equipment from Braukmann GmbH, Germany (Caso®VC10 Vakuumierer) is used for the welding process, and the material isallowed to cool at room temperature for hardening.

For accelerated ageing, the samples are stored uncovered in aluminiumdishes in a drying cabinet for 7 days at 60° C.

The shelf life of the samples is evaluated on the basis of the remainingcontent of VP Si 363 monomer in comparison with oligomeric structures byusing ²⁹Si NMR measurements. The results are shown in Table 2.

The ²⁹Si NMR measurements are made in a 500 MHz “Bruker Avance 500” fromBruker with nitrogen-cooled cryohead (about 2000 scans). For preparationof the samples of the silane/wax mixture and, respectively, silanecarbon black mixture, about 0.5 g of the sample is added to a Brandculture tube with screw closure, from 3 to 4 mL of CDCl₃ and Cr(acac)₃are added, and the mixture is treated three times for 15 minutes in aPanasonic 470/H ultrasound bath. It is then centrifuged and alsofiltered. An NMR spectrum of the solution is then recorded.

TABLE 2 Monomer content [mol %] Monomer content prior to [mol %] storageafter storage Comparative Example 2 97 87 Comparative Example 3 97Sachet unstable Comparative Example 4 98 <5% Inventive Example 2: 97 95Inventive Example 3: 97 96

The results show that the sachet markedly increases shelf life whencomparison is made with the uncovered wax-silane mixtures. InventiveExamples 2 and 3 with film thicknesses of 150 μm lead to greaterstability in comparison with Comparative Example 3, in which the sachetburst during storage. There is also a significant improvement of shelflife in comparison with the carbon-black-based Comparative Example 4.

Example 3: (Comparison of Carbon Black and Wax/Sachet as Carrier)

The formulation used for the rubber mixtures is specified in Table 3below. The unit phr here means parts by weight based on 100 parts of thecrude rubber used. Each of the rubber mixtures uses an equimolecularquantity of VP Si 363 silane.

TABLE 3 Quantity Quantity Substance Quantity [phr] [phr] [phr] 1st stageRef. Ref. Inv. rubber Rubber Rubber mixture I mixture II mixture IIIBuna VSL 96.25 96.25 96.25 5025-2 Buna CB 24 30 30 30 ULTRASIL 80 80 807000 GR Corax ® N 330 5 — 5 ZnO RS 2 2 2 Edenor ST1 1 1 1 Vivatec 5008.75 8.75 8.75 Protector 2 2 2 G 3108 Vulkanox 4020/LG 2 2 2Vulkanox-HS/LG 1.5 1.5 1.5 VP Si 363 ® 9 — — Comparative — 18 — Example4 Inventive — — 10.80 Example 3 2nd Stage Stage 1 batch 3rd stage Stage2 batch Perkacit 0.4 0.4 0.4 TBzTD Vulkacit CZ/EG-C 1.6 1.6 1.6 Sulphur2.0 2.0 2.0

The polymer VSL 5025-2 is a solution-polymerized SBR copolymer fromLanxess AG, with 25% by weight styrene content and with 50% by weightvinyl fraction. The copolymer comprises 37.5 phr of TDAE oil and itsMooney viscosity (ML 1+4/100° C.) is 47 MU.

The polymer Buna CB 24 is a high-cis-1,4-polybutadiene (neodymium type)from Lanxess AG, with at least 96% cis-1,4 content and with Mooneyviscosity of 44+5 MU.

Ultrasil 7000 GR is a readily dispersible silica from Evonik IndustriesAG with BET surface area of 170 m²/g.

The carbon black Corax N 330 is from Orion Engineered Carbons GmbH.Vivatec 500 from H&R AG is used as TDAE oil, Vulkanox 4020/LG is 6PPDfrom Rhein Chemie Rheinau GmbH, Vulkanox HS/LG is TMQ from Rhein ChemieRheinau GmbH and Protektor G3108 is an antiozonant wax from ParameltB.V., ZnO RS is ZnO from Arnsperger Chemikalien GmbH, EDENOR ST1 GS 2.0is palmitic-stearic acid from Caldic Deutschland Chemie B.V. andVulkacit CZ/EG-C is CBS from Chemie Rheinau GmbH. TBzTD was purchasedvia Weber & Schaer (producer: Dalian Richon).

The mixtures were produced in three stages in a 1.5 l internal mixer (Etype) with batch temperature 155° C. according to the mixingspecification described in Table 4.

TABLE 4 Stage 1 Settings Mixing from HF Mixing Group GmbH; type GK 1,5 Eassembly Fill level 0.65 Rotation rate 70 min⁻¹ Ram pressure 5.5 barChamber temp. 70° C. Mixing procedure 0 to 0.5 min Buna VSL 5025-2 +Buna CB 24 0.5 min TMQ, 6PPD 0.5 to 1 min Mix 1 to 2 min ½ ULTRASIL 7000GR, silane or silane on HS 45 or plastics-covered mercaptosilane- waxmixture, ZnO, stearic acid 2 min Purge and ventilate 2 to 3 min Carbonblack, Vivatec 500, ½ ULTRASIL 7000 GR, Protector G3108 3 min Purge andventilate 3 to 5 min Mix at 155° C. 5 min Discharge and form milledsheet on laboratory roll mill for 45 s (Laboratory roll mill: diameter250 mm, length 190 mm, gap between rolls 4 mm, roll temperature 60° C.)24 h at room temperature Stage 2 Settings Mixing as in stage 1 exceptassembly Fill level 0.62 Mixing procedure 0 to 0.5 min Break up stage 1batch 0.5 to 3 min Mix at 155° C. 3 min Discharge and form milled sheeton laboratory roll mill for 45 s (Laboratory roll mill: diameter 250 mm,length 190 mm, gap between rolls 4 mm, roll temperature 60° C.) 4 h atroom temperature Stage 3 Settings Mixing as in stage 1 except assemblyFill level 0.59 Rotation rate 50 min⁻¹ Chamber temp. 50° C. Mixingprocedure 0 to 0.5 min Break up stage 2 batch 0.5 to 2 min Acceleratorand sulphur, mix at 100° C. 2 min Discharge and form milled sheet onlaboratory roll mill for 20 s, and within a further 40 s: cut thematerial and fold it over 3* towards the left and 3* towards the right,and roll the material 3* with narrow roll gap (3 mm) and draw off milledsheet. (Laboratory roll mill: diameter 250 mm, length 190 mm, gapbetween rolls from 3 to 4 mm, roll temperature 80° C.) Batch temp. 100°C.

The general process for the production of rubber mixtures andvulcanizates of these is described in “Rubber Technology Handbook”, W.Hofmann, Hanser Verlag 1994.

Table 5 gives the rubber testing methods used.

Vulcanization takes place at a temperature of 165° C. for a period of 8minutes in a typical vulcanization press with a retention pressure of120 bar. Table 6 gives the data for crude mixture and vulcanizate.

TABLE 5 Physical testing Standard/conditions Mooney viscosity ML 1 + 4at 100° C. ISO 289-1 Mooney viscosity/MU Rheovulcameter measurements at100° C. Volume after 30 s/mm³ Rheo-Vulkameter 78.90 Apparent shearrate/s⁻¹ (Gottfert Werkstoff- Apparent viscosity/Pa s PrufmaschinenGmbH) Nozzle 2 mm × 10 mm test pressure 40 bar, preheat time 60 sTensile test on specimen at 23° C. ISO 37 Reinforcement index: 300%modulus/50% modulus Shore A hardness at 23° C. ISO 7619-1 Shore Ahardness/SH Ball rebound, 23° C. and 70° C. DIN EN ISO 8307 Reboundresilience/% Drop height 500 mm, steel ball d = 19 mm, 28 g Viscoelasticproperties of Rubber Process Analyser vulcanizate at 60° C. RPA 2000(Alpha Technologies), Strain Sweep, 1.7 Hz, 0.28%-42% elongation; see“Operators Manual RPA 2000” from Alpha Technologies, Feb. 1997 Maximumloss factor tan δ Viscoelastic properties at 60° C. ISO 4664-1 16 Hz, 50N initial force and 25 N amplitude force, 5 min temperature-adjustmenttime, measured value recorded after 30 s of test time Loss factor tan δ

TABLE 6 Ref. Ref. Inv. rubber rubber rubber mixture I mixture II mixtureIII Crude mixture results: Mooney viscosity ML 1 + 4 at 100° C. Mooneyviscosity/MU 1st stage 129   129   120   2nd Stage 80   82   78   3rdstage 54   55   53   Rheovulcameter measurements at 100° C. Volume after30 s/mm³ 1st stage 413   548   577   2nd stage 1067    1010    1125   3rd stage 2058    1933    2201    Apparent shear rate/s⁻¹ 1st stage 18.224.6 26.5 2nd stage 47.4 45.0 49.2 3rd stage 91.1 82.9 95.1 Apparentviscosity/Pa s 1st stage 16 234    12 021    11 141    2nd stage 6229   6570    6010    3rd stage 3244    3564    3106    Vulcanizate results:Tensile test on specimen at 23° C. Reinforcement index 300%/50% modulus10.2 10.5 11.0 Shore A hardness/SH 55   56   55   Ball rebound Reboundresilience at 43.6 43.1 43.4 23° C./% Rebound resilience at 72.3 71.574.6 70° C./% Difference: Rebound res. 28.7 28.4 31.2 70° C. − reboundres. 23° C./% Viscoelastic properties, 60° C. Rubber Process Analyser(RPA), Strain Sweep, 1.7 Hz, 0.28%-42% elongation Maximum loss factortan δ/—   0.116   0.114   0.104 Viscoelastic properties at 60° C., 16Hz, 50 N initial force, 25 N amplitude force Loss factor tan δ/—   0.094  0.093   0.090

In comparison with Comparative Mixture I with VP Si 363 alone andComparative Mixture II according to WO2013149790, the rubber mixture IIIof the invention exhibits improved processing behaviour (in all threemixing stages lower Mooney and apparent viscosities, higher shear rates,and also volumes after 30 s), improved reinforcement behaviour (higherreinforcement index), improved rolling resistance (lower tan δ values at60° C., higher rebound resilience at 60° C.) and better realization ofthe trade-off between wet skid and rolling resistance (differencebetween rebound resilience values at 70° C. and at 23° C.).

The invention claimed is:
 1. A sealed plastics-coveredmercaptosilane-wax mixture, comprising a plastics covering, selectedfrom the group consisting of polypropylene, polyethylene, ethylene-vinylacetate copolymer, and mixtures of the above mentioned plastics withmelting point from 70 to 170° C., and mercaptosilane-wax mixturecomprises at least one mercaptosilane, a monomer, of the general formulaI

where R¹ is an alkyl polyether group —O—(R⁵—O)_(m)—R⁶, where R⁵ isidentical or different and is a branched or unbranched, saturated orunsaturated, aliphatic divalent C1-C30 hydrocarbon group, m is onaverage from 1 to 30, and R⁶ is composed of at least 1 C atom and is anunsubstituted or substituted, branched or unbranched monovalent alkyl,alkenyl, aryl or aralkyl group, R² is identical or different and is anR¹, C1-C12-alkyl or R⁷O group, where R⁷ is H, methyl, ethyl, propyl,C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl, oraralkyl group or (R⁸)₃Si group, where R⁸ is C1-C30 branched orunbranched alkyl or alkenyl group, R³ is a branched or unbranched,saturated or unsaturated, aliphatic, aromatic or mixedaliphatic/aromatic divalent C1-C30 hydrocarbon group and R⁴ is H, CN or(C═O)—R⁹, where R⁹ is a branched or unbranched, saturated orunsaturated, aliphatic, aromatic or mixed aliphatic/aromatic monovalentC1-C30 hydrocarbon group, and at least one wax with congealing pointfrom 30 to 160° C., wherein the plastics-covering has a thickness of theplastics covering is from 10 to 3000 μm and is a sachet and themercaptosilane-wax mixture has a ratio by weight of mercaptosilane ofgeneral formula I to wax from 10:90 to 95:5 and, wherein the plastic hasan average molar mass of the plastic of the plastics covering is from 50000 to 1 000 000 g/mol.
 2. The plastics-covered mercaptosilane-waxmixture according to claim 1, wherein the mercaptosilane-wax mixturecomprises a mixture of mercaptosilanes of the general formula I.
 3. Theplastics-covered mercaptosilane-wax mixture according to claim 2,wherein the mixture of mercaptosilanes of the general formula (I)comprises and,


4. A process for the production of the sealed plastics-coveredmercaptosilane-wax mixture according to claim 1, comprising mixing of atleast one mercaptosilane of the general formula I with at least one waxwith congealing point from 30 to 160° C. to form a mercaptosilane-waxmixture having a ratio by weight of mercaptosilane of general formula Ito wax from 55:45 to 90:10, and charging the mercaptosilane-wax mixtureto a plastics sachet, where the plastic of the sachet is selected fromthe group of polypropylene, polyethylene, ethylene-vinyl acetatecopolymer and mixtures of the abovementioned plastics with melting pointfrom 70 to 170° C., and sealing the plastics sachet.
 5. The processaccording to claim 4, wherein mixing includes a process involving atemperature-controllable kneading, stirring, or mixing assembly.
 6. Theprocess according to claim 4, wherein mixing occurs at temperatures offrom 30 to 160° C.
 7. The process according to claim 4, wherein chargingtakes place at temperatures of from 30 to 160° C.
 8. A method for theproduction of rubber mixtures comprising: introducing theplastics-covered mercaptosilane-wax mixture according to claim 1 to amixture having at least one rubber.
 9. A rubber mixture comprising: (A)at least one rubber, (B) at least one filler, and (C) at least onesealed plastics-covered mercaptosilane-wax mixture according to claim 1.